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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o449.
Published online 2009 February 4. doi:  10.1107/S1600536809003742
PMCID: PMC2968464

Methyl 2-(N-methoxy­carbonyl­meth­yl-N-methylsulfamo­yl)benzoate

Abstract

In the title compound, C12H15NO6S, the aromatic ring is oriented at dihedral angles of 64.76 (11) and 56.42 (13)° with respect to the planar methyl ester unit and the SO2 group, respectively. The dihedral angle between the SO2 group and the planar methoxy­carbonyl­methyl group is 50.42 (14)°. Intra­molecular C—H(...)O hydrogen bonding results in the formation of an eight-membered ring. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules.

Related literature

For general background, see: Hanson et al. (1999 [triangle]). For related structures, see: Arshad et al. (2008 [triangle]); Shafiq et al. (2008a [triangle],b [triangle]); Ma et al., 2003 [triangle]).

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Object name is e-65-0o449-scheme1.jpg

Experimental

Crystal data

  • C12H15NO6S
  • M r = 301.31
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o449-efi1.jpg
  • a = 8.5830 (3) Å
  • b = 9.0966 (3) Å
  • c = 18.3329 (7) Å
  • V = 1431.36 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 296 (2) K
  • 0.22 × 0.18 × 0.15 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.942, T max = 0.965
  • 16627 measured reflections
  • 3558 independent reflections
  • 2513 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.098
  • S = 1.01
  • 3558 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.24 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1509 Friedel pairs
  • Flack parameter: 0.12 (8)

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003742/hk2618sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003742/hk2618Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

NA gratefully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing his Scholarship under the Indigenous PhD Program (PIN 042–120599-PS2–156).

supplementary crystallographic information

Comment

Sulfonamides are a class of compounds, which find wide applications in medicinal chemistry (Hanson et al., 1999). Cyclic sulfonamides (benzothiazine) have biological activities such as lipoxygenase inhibition, and they are used as drugs for heart diseases. We are engaged in the syntheses of various derivatives of benzothiazine molecule (Arshad et al., 2008; Shafiq et al., 20082008a,b). We report herein the crystal structure of the title compound, (I), which is used as an intermediate for further syntheses.

In the molecule of the title compound, (I), (Fig. 1), the coordination around the S atom is a distorted tetrahedral. The crystal structure of methyl 2-(4-methoxypyrimidin-2-ylcarbamoylsulfamoyl)benzoate, (II) (Ma et al., 2003) has been reported, which also has a sulfamoylbenzoate moiety. In (I), the benzene ring A (C1-C6) is oriented with respect to the planar methyl ester moiety (O1/O2/C7/C8) and SO2 group at dihedral angles of 64.76 (11)° and 56.42 (13)°, respectively. The dihedral angle between SO2 moiety and the planar methoxycarbonylmethyl group (O5/O6/N1/C9/C10/C12) is 50.42 (14)°. Intramolecular C—H···O hydrogen bonding (Table 1) results in the formation of an eight-membered ring (S1/O1/N1/C1/C6/C7/C9/H9A).

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, sodium saccharine (20.5 g, 0.1 mol) and methylchloroacetic acid (10.85 g, 0.1 mol) were dissolved in DMF (50 ml) and refluxed for 1 h, and then ice was added for precipitation. The precipitate (12.8 g, 0.05 mol) was dissolved in methanol (50 ml), and sodium methoxide (5.4 g, 0.1 mol) was added, and then refluxed for 3 h. The volume was reduced to half by evaporation. Then, HCl was added on cooling and left overnight in refrigerator, which was then recrystallized from absolute ethanol.

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.96 and 0.97 Å for aromatic, methyl and methylene group and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dotted line.
Fig. 2.
A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H15NO6SF(000) = 632
Mr = 301.31Dx = 1.398 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3558 reflections
a = 8.5830 (3) Åθ = 2.2–28.3°
b = 9.0966 (3) ŵ = 0.25 mm1
c = 18.3329 (7) ÅT = 296 K
V = 1431.36 (9) Å3Prism, colorless
Z = 40.22 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer3558 independent reflections
Radiation source: fine-focus sealed tube2513 reflections with I > 2σ(I)
graphiteRint = 0.039
Detector resolution: 7.40 pixels mm-1θmax = 28.3°, θmin = 2.2°
ω scansh = −11→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −12→10
Tmin = 0.942, Tmax = 0.965l = −24→24
16627 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.098w = 1/[σ2(Fo2) + (0.0476P)2 + 0.0688P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3558 reflectionsΔρmax = 0.16 e Å3
184 parametersΔρmin = −0.24 e Å3
0 restraintsAbsolute structure: Flack (1983), 1509 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.12 (8)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.48790 (6)0.03278 (6)0.16077 (3)0.0454 (2)
O10.78607 (18)0.0316 (2)0.03285 (9)0.0594 (6)
O20.8987 (2)−0.15351 (18)0.09228 (8)0.0578 (6)
O30.5106 (2)−0.09093 (17)0.11432 (8)0.0528 (5)
O40.3864 (2)0.0227 (2)0.22151 (9)0.0730 (7)
O50.1989 (2)0.0586 (2)0.01831 (11)0.0744 (8)
O60.3568 (3)0.0937 (2)−0.07700 (10)0.0802 (8)
N10.4279 (2)0.1681 (2)0.11144 (10)0.0534 (7)
C10.6735 (3)0.0822 (2)0.19630 (11)0.0437 (7)
C20.6751 (3)0.1563 (3)0.26251 (12)0.0581 (8)
C30.8149 (4)0.1958 (3)0.29366 (16)0.0783 (11)
C40.9518 (4)0.1598 (3)0.26066 (17)0.0883 (12)
C50.9524 (3)0.0831 (3)0.19607 (15)0.0705 (10)
C60.8129 (3)0.0454 (2)0.16210 (12)0.0453 (7)
C70.8263 (2)−0.0253 (3)0.08873 (12)0.0451 (7)
C80.9334 (3)−0.2224 (3)0.02298 (14)0.0691 (10)
C90.4512 (3)0.1665 (3)0.03348 (12)0.0551 (8)
C100.3184 (3)0.0993 (3)−0.00666 (13)0.0524 (8)
C110.3366 (4)0.2883 (3)0.14377 (16)0.0815 (11)
C120.2408 (5)0.0357 (5)−0.12639 (17)0.1163 (16)
H20.581870.179130.285770.0698*
H30.815830.247360.337470.0940*
H41.045650.187420.282000.1058*
H51.046660.056090.174910.0846*
H8A0.83789−0.24343−0.002230.1037*
H8B0.98933−0.312250.031230.1037*
H8C0.99584−0.15722−0.006000.1037*
H9A0.545470.112010.022500.0661*
H9B0.465770.266580.016530.0661*
H11A0.374750.380790.126020.1224*
H11B0.346310.285200.195910.1224*
H11C0.229010.277310.130490.1224*
H12A0.21196−0.06164−0.111280.1744*
H12B0.282840.03215−0.174880.1744*
H12C0.150560.09800−0.125800.1744*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0541 (3)0.0436 (3)0.0386 (3)−0.0130 (3)0.0029 (3)−0.0013 (3)
O10.0599 (9)0.0687 (12)0.0497 (9)0.0096 (9)0.0026 (8)0.0119 (9)
O20.0758 (11)0.0440 (10)0.0535 (10)0.0095 (9)−0.0038 (8)−0.0040 (8)
O30.0687 (10)0.0402 (8)0.0495 (8)−0.0140 (8)−0.0024 (9)−0.0063 (7)
O40.0796 (11)0.0836 (13)0.0558 (10)−0.0252 (11)0.0226 (9)−0.0036 (10)
O50.0505 (10)0.0879 (16)0.0849 (13)−0.0031 (10)−0.0139 (10)−0.0223 (12)
O60.1054 (14)0.0852 (14)0.0501 (11)0.0268 (12)−0.0149 (10)−0.0049 (10)
N10.0599 (11)0.0491 (12)0.0511 (11)0.0039 (9)−0.0131 (9)−0.0068 (10)
C10.0611 (13)0.0340 (12)0.0360 (11)−0.0023 (10)−0.0100 (10)0.0024 (9)
C20.0782 (16)0.0507 (15)0.0455 (13)0.0060 (14)−0.0108 (12)−0.0074 (12)
C30.100 (2)0.069 (2)0.0658 (18)0.0140 (18)−0.0382 (17)−0.0274 (15)
C40.084 (2)0.077 (2)0.104 (2)0.0090 (17)−0.0509 (18)−0.0333 (19)
C50.0603 (15)0.0640 (18)0.0873 (19)0.0066 (13)−0.0235 (14)−0.0177 (15)
C60.0534 (11)0.0350 (13)0.0476 (12)0.0020 (10)−0.0107 (11)−0.0001 (11)
C70.0418 (11)0.0428 (13)0.0506 (13)−0.0012 (10)−0.0020 (10)0.0018 (11)
C80.0825 (18)0.0591 (18)0.0657 (16)0.0050 (14)0.0069 (14)−0.0177 (14)
C90.0541 (13)0.0553 (16)0.0559 (14)−0.0002 (11)−0.0089 (11)0.0131 (12)
C100.0553 (14)0.0493 (14)0.0526 (15)0.0177 (12)−0.0147 (12)−0.0042 (12)
C110.0798 (19)0.0618 (19)0.103 (2)0.0132 (16)−0.0086 (17)−0.0203 (17)
C120.148 (3)0.124 (3)0.077 (2)0.057 (3)−0.064 (2)−0.044 (2)

Geometric parameters (Å, °)

S1—O31.4246 (16)C6—C71.495 (3)
S1—O41.4168 (18)C9—C101.488 (4)
S1—N11.6119 (19)C2—H20.9300
S1—C11.779 (3)C3—H30.9300
O1—C71.199 (3)C4—H40.9300
O2—C71.323 (3)C5—H50.9300
O2—C81.448 (3)C8—H8A0.9600
O5—C101.183 (3)C8—H8B0.9600
O6—C101.332 (3)C8—H8C0.9600
O6—C121.446 (4)C9—H9A0.9700
N1—C91.443 (3)C9—H9B0.9700
N1—C111.470 (3)C11—H11A0.9600
C1—C21.389 (3)C11—H11B0.9600
C1—C61.392 (3)C11—H11C0.9600
C2—C31.377 (4)C12—H12A0.9600
C3—C41.362 (5)C12—H12B0.9600
C4—C51.374 (4)C12—H12C0.9600
C5—C61.393 (4)
S1···O13.4712 (17)C9···O13.125 (3)
O1···S13.4712 (17)C9···O1v3.321 (3)
O1···O33.011 (2)C9···O5i3.417 (3)
O1···C93.125 (3)C10···O33.261 (3)
O1···C9i3.321 (3)C10···C8ii3.580 (4)
O1···C10i3.403 (3)C10···O1v3.403 (3)
O3···O13.011 (2)C11···O53.325 (3)
O3···C8ii3.108 (3)C12···O4x3.041 (4)
O3···C72.814 (2)C7···H9A2.9700
O3···C103.261 (3)C10···H11C3.0900
O4···C12iii3.041 (4)C10···H8Bii3.0300
O4···C2iv3.387 (3)C11···H12Ci2.9100
O5···N12.788 (3)H2···O42.5000
O5···C113.325 (3)H2···O3viii2.8900
O5···C9v3.417 (3)H3···O2xi2.9100
O1···H8C2.5900H4···O2xi2.7600
O1···H9Bi2.5600H5···O22.7500
O1···H8A2.6200H8A···O12.6200
O1···H9A2.2000H8B···O3ix2.8200
O2···H4vi2.7600H8B···C10ix3.0300
O2···H52.7500H8C···O12.5900
O2···H3vi2.9100H8C···O5xii2.6600
O3···H2iv2.8900H9A···O12.2000
O3···H8Bii2.8200H9A···O32.5200
O3···H9A2.5200H9A···C72.9700
O4···H22.5000H9B···H11A2.3900
O4···H11B2.4600H9B···O1v2.5600
O4···H12Biii2.4400H9B···O5i2.6300
O5···H8Cvii2.6600H11A···H9B2.3900
O5···H12A2.6200H11A···H12Ci2.3800
O5···H12C2.7000H11B···O42.4600
O5···H11C2.8700H11C···O52.8700
O5···H9Bv2.6300H11C···C103.0900
N1···O52.788 (3)H12A···O52.6200
N1···H12Ci2.8700H12B···O4x2.4400
C2···O4viii3.387 (3)H12C···O52.7000
C7···O32.814 (2)H12C···N1v2.8700
C8···O3ix3.108 (3)H12C···C11v2.9100
C8···C10ix3.580 (4)H12C···H11Av2.3800
O3—S1—O4120.18 (10)C2—C3—H3120.00
O3—S1—N1108.15 (10)C4—C3—H3120.00
O3—S1—C1107.22 (10)C3—C4—H4120.00
O4—S1—N1107.09 (10)C5—C4—H4120.00
O4—S1—C1106.21 (10)C4—C5—H5120.00
N1—S1—C1107.37 (9)C6—C5—H5120.00
C7—O2—C8115.79 (18)O2—C8—H8A109.00
C10—O6—C12116.7 (3)O2—C8—H8B109.00
S1—N1—C9120.24 (16)O2—C8—H8C109.00
S1—N1—C11120.81 (16)H8A—C8—H8B109.00
C9—N1—C11118.7 (2)H8A—C8—H8C109.00
S1—C1—C2116.85 (19)H8B—C8—H8C110.00
S1—C1—C6122.97 (16)N1—C9—H9A109.00
C2—C1—C6120.1 (2)N1—C9—H9B109.00
C1—C2—C3119.9 (2)C10—C9—H9A109.00
C2—C3—C4120.3 (3)C10—C9—H9B109.00
C3—C4—C5120.5 (3)H9A—C9—H9B108.00
C4—C5—C6120.5 (3)N1—C11—H11A109.00
C1—C6—C5118.6 (2)N1—C11—H11B109.00
C1—C6—C7125.1 (2)N1—C11—H11C109.00
C5—C6—C7116.2 (2)H11A—C11—H11B109.00
O1—C7—O2123.9 (2)H11A—C11—H11C109.00
O1—C7—C6124.1 (2)H11B—C11—H11C109.00
O2—C7—C6111.78 (18)O6—C12—H12A109.00
N1—C9—C10112.8 (2)O6—C12—H12B109.00
O5—C10—O6125.3 (2)O6—C12—H12C109.00
O5—C10—C9127.0 (2)H12A—C12—H12B109.00
O6—C10—C9107.8 (2)H12A—C12—H12C109.00
C1—C2—H2120.00H12B—C12—H12C109.00
C3—C2—H2120.00
O3—S1—N1—C9−19.1 (2)S1—C1—C2—C3179.0 (2)
O3—S1—N1—C11155.37 (19)C6—C1—C2—C31.2 (3)
O4—S1—N1—C9−149.96 (17)S1—C1—C6—C5−176.98 (17)
O4—S1—N1—C1124.5 (2)S1—C1—C6—C76.6 (3)
C1—S1—N1—C996.32 (18)C2—C1—C6—C50.7 (3)
C1—S1—N1—C11−89.2 (2)C2—C1—C6—C7−175.8 (2)
O3—S1—C1—C2−154.78 (17)C1—C2—C3—C4−1.4 (4)
O3—S1—C1—C622.94 (19)C2—C3—C4—C5−0.3 (4)
O4—S1—C1—C2−25.1 (2)C3—C4—C5—C62.2 (4)
O4—S1—C1—C6152.60 (17)C4—C5—C6—C1−2.4 (4)
N1—S1—C1—C289.20 (19)C4—C5—C6—C7174.4 (2)
N1—S1—C1—C6−93.09 (18)C1—C6—C7—O164.8 (3)
C8—O2—C7—O12.1 (3)C1—C6—C7—O2−120.0 (2)
C8—O2—C7—C6−173.08 (19)C5—C6—C7—O1−111.8 (2)
C12—O6—C10—O51.3 (4)C5—C6—C7—O263.4 (3)
C12—O6—C10—C9−178.1 (3)N1—C9—C10—O55.0 (4)
S1—N1—C9—C1091.0 (2)N1—C9—C10—O6−175.5 (2)
C11—N1—C9—C10−83.6 (3)

Symmetry codes: (i) x+1/2, −y+1/2, −z; (ii) x−1/2, −y−1/2, −z; (iii) −x+1/2, −y, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x−1/2, −y+1/2, −z; (vi) −x+2, y−1/2, −z+1/2; (vii) x−1, y, z; (viii) −x+1, y+1/2, −z+1/2; (ix) x+1/2, −y−1/2, −z; (x) −x+1/2, −y, z−1/2; (xi) −x+2, y+1/2, −z+1/2; (xii) x+1, y, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···O10.972.203.125 (3)159
C9—H9B···O1v0.972.563.321 (3)135
C12—H12B···O4x0.962.443.041 (4)120

Symmetry codes: (v) x−1/2, −y+1/2, −z; (x) −x+1/2, −y, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2618).

References

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  • Bruker (2005). SADABS Bruker AXS Inc. Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Hanson, P. R., Probst, D. A., Robinson, R. E. & Yau, M. (1999). Tetrahedron Lett.40, 4761–4764.
  • Ma, N., Wang, B., Wang, J., Song, H., Wang, S. & Li, Z. (2003). Acta Cryst. E59, o438–o440.
  • Shafiq, M., Khan, I. U., Tahir, M. N. & Siddiqui, W. A. (2008a). Acta Cryst. E64, o558. [PMC free article] [PubMed]
  • Shafiq, M., Tahir, M. N., Khan, I. U., Ahmad, S. & Siddiqui, W. A. (2008b). Acta Cryst. E64, o1270. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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